EP0276756B1 - Filaments composites conductifs et articles fibreux contenant ces filaments - Google Patents
Filaments composites conductifs et articles fibreux contenant ces filaments Download PDFInfo
- Publication number
- EP0276756B1 EP0276756B1 EP88100844A EP88100844A EP0276756B1 EP 0276756 B1 EP0276756 B1 EP 0276756B1 EP 88100844 A EP88100844 A EP 88100844A EP 88100844 A EP88100844 A EP 88100844A EP 0276756 B1 EP0276756 B1 EP 0276756B1
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- EP
- European Patent Office
- Prior art keywords
- conductive
- filament
- sheath
- core
- component
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05F—STATIC ELECTRICITY; NATURALLY-OCCURRING ELECTRICITY
- H05F3/00—Carrying-off electrostatic charges
- H05F3/04—Carrying-off electrostatic charges by means of spark gaps or other discharge devices
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
Definitions
- the present invention relates to novel conductive composite filaments, more particularly, conductive composite filaments which are industrially easily manufacturable, having substantially no metal abrasive property, and further relates to antistatic fibrous articles containing the same.
- fibers particularly, hydrophobic fibers consisting of polyester, polyamide, polyacrylonitrile, polyolefin or the like, generate a lot of static electricity due to friction, etc., often exceeding 10 kV, which causes various troubles. Therefore, many proposals relating to destaticization (imparting of antistatic properties) have been made.
- the metallic fibers have shortcomings, such as brittleness to induce breakages by bending during processing and using, which cause a decrease in antistatic property. Also the metallic fibers are difficult in blending, mixed weaving or mixed knitting with other fibers and, moreover, have an inherent metallic luster that impairs the quality of articles when the metallic fibers are incorporated therewith.
- metal deposited fibers and conductive material coated fibers also have many drawbacks, such as an extremely high cost of production, a low durability owing to liability to detachment of the coating by bending or due to friction during processing and using, or the like.
- conductive particles for example, carbon black, metal particles, etc.
- composite filaments in which a conductive component composed of a thermoplastic polymer containing conductive particles, for example, carbon black, metal particles, etc., dispersed therein and a non-conductive component of a fiber-forming thermoplastic polymer are bonded together in a side by side or sheath-core relationship uniformly extending along the longitudinal axis of the filament have been proposed in the gazettes of Japanese Patent Application Publication Nos. 31,450/77, 44,579/78 and 25,647/82, Japanese Patent Application Laid-open No. 60-224,813, etc.
- sheath-core type composite filaments those having a non-conductive component completely encapsulating a conductive particles containing conductive component, since dielectric breakdown in the sheath portion to induce corona discharge hardly occurs, have a shortcoming that is a poor antistatic property.
- these composite filaments exhibit noticeable black or dark grey color of carbon black or inorganic conductive particles, deteriorate the appearance of articles containing these filaments.
- these composite filaments having a hard conductive particles containing conductive component exposed on the filament surface when the filaments travel as rubbing upon a stationary body, abrade and eventually mar the body due to friction. Therefore, such composite filaments thus provided with an augmented metal abrasive property are involved in serious problems in the course of manufacturing and processing.
- the gazette of Japanese Patent Application Laid-open No. 60-110,920 discloses a core and thin skin type composite filament that comprises a skin component having the thinnest portions of 3 ⁇ m or less on the cross section.
- This filament is very excellent for obviating the metal abrasive property as well as providing the antistatic property.
- the non-conductive skin is made thin enough to provide a satisfactory antistatic property, the skin becomes liable to break, resulting in metal abrasion by the uncovered core. Accordingly, this type of filament still poses a problem such that stable manufacture is difficult to be performed.
- the gazette of Japanese Patent Application Laid-open No.60-224,812 discloses an improved core and thin skin type composite filament, where the skin is composed of a fiber-forming polymer having conductive particles of metal oxide or metal compound, and more preferably the particle size satisfies the formula; 0.5 ⁇ size of conductive particle/minimum thickness of skin ⁇ 4.
- the conductive particles in the skin are contained much enough to provide a satisfactory antistatic property, the color or metal abrasion is revealed again.
- a conductive composite filament prepared by conjugating a mixture (A) consisting of a conductive polymer composition (P1 ⁇ ) and a fiber-forming thermoplastic polymer (P2) which is incompatible with (P1 ⁇ ) with non-conductive fiber-forming thermoplastic polymer.
- the mixture (A) occupies part of the surface area of the filament and part of (P1 ⁇ ) comes up to the surface in the lengthwise direction of the filament through an opening.
- a conductive composite filament in fact, is unstable in yarn-spinnability and, moreover, insufficient in electroconductivity for lack of a conductive core as in the Case of Comparative Example Y17 that will be described hereinafter.
- GB-A-2 077 182 discloses a conductive composite filament comprising a conductive component composed of conductive metal oxide particles in a thermoplastic polymer and/or a solvent soluble polymer bonded along the length of the filament to a non-conductive component composed of a fiber-forming polymer.
- An object of the present invention is to provide improved conductive composite filaments which have high whiteness, excellent antistatic property, exhibiting no abrasive property, which can be commercially easily manufactured.
- Another object of the present invention is to provide fibrous articles with excellent antistatic property and aesthetic appearance which contain the conductive composite filaments of the invention.
- a unitary conductive composite filament which comprises:
- the cross-sectional figure of the composite filaments according to the present invention is not specifically limited. It may be either circular or non-circular, but the circular one is preferred.
- the cross-sectional figure of the conductive component is important.
- the conductive component has a tadpole-like shape consisting of a head of the conductive core 1 having a thickness of not less than 5 ⁇ m and a tail of the conductive path 2 both lapped in a sheath 3 composed of a non-conductive component extending along the entire length of the filament.
- the conductive path 2 extends laterally from a part of the periphery of said head of the conductive core 1, transversely through the sheath 3, up to or close to the outer circumference of the sheath. Longitudinally, it extends along the entire length of said core in such a manner that the conductive path is exposed intermittently along the longitudinal axis of the filament and not more than 1.5 ⁇ m in width on the outer peripheral surface of the sheath.
- the conductive component has a tadpole-like figure which is composed of the conductive core as its head and the conductive path as its tail.
- the conductive core embedded in the sheath is positioned nearly in the center of the filament and only the tip of the conductive path barely reaches the circumference of the filament.
- the thick conductive core extends continuously along the length of the filament and the thin conductive path is exposed intermittently lengthwise on the surface of the filament.
- the cross-sectional figure of the conductive core may be arbitrarily selected from circular, elliptical, triangular, rectangular or the like.
- the conductive core occupies a major portion, for example, at least 60% by volume, of the conductive component. Its thickness, for example, d1 in FIG. 1, is at least 5 ⁇ m. There may be either case where the core is clearly distinguishable (e.g., FIG. 1) or indistinguishable (e.g., FIGS. 2 and 5).
- the conductive path means a thin portion conjoined with the conductive core. Its cross-sectional figure may be straight and, however, a bent or crooked one is more preferred for narrowing the exposed width of its tip. Additionally, from the joint with the conductive core to the tip, of the conductive path, the thicknesses may be substantially same (FIG. 1) and, however, those gradually attenuated (FIGS. 2, 4 and 5) or thin-and-thick (FIG. 6) are preferred for controlling the exposed width narrow as desired. In contrast, when the conductive component consists solely of a thin band without having a core (thick portion) as shown in FIG. 10, the electric conductivity or antistatic property is apt to decrease or become unstable, while, if it is formed thick, the metal abrasive property will increase appreciably, so that this type of the conductive component is not suitable.
- the width of the conductive path that is exposed on surfaces of the filament is not more than 1.5 ⁇ m, preferably not more than 1.2 ⁇ m, most preferably not more than 1.0 ⁇ m. If the exposed width is too large, the metal abrasion becomes liable to occur.
- the conductive path is exposed lengthwise intermittently on the surface of the filament.
- the portion to be exposed is the tip or a part of its vicinity of the conductive path.
- the length along the longitudinal axis of the filament of the exposed portion is not specifically defined.
- the proportion of the exposed length to the entire length of the filament is preferably not more than 90%, more preferably not more than 70%, most preferably not more than 50%. Too large the width or the length proportion of the exposed portion tends to cause metal abrasion.
- the composite filaments according to the present invention have a novel cross-sectional figure that is quite different from those of any conventional sheath-core or side by side type conductive composite filaments.
- the conjugate ratio that is, the area ratio occupied by the conductive component in the cross-section of the composite filaments is preferably 3-40%, more preferably 4-20%, most preferably 5-15%.
- the conjugate ratio is too small, the conductivity will decrease, lessening therefore the antistatic property.
- it is too large physical or mechanical properties of the filaments will be deteriorated and the metal abrasive property will be augmented.
- any kind of particles can be employed insofar as they have a specific resistance in powdery form of not more than about 104 ⁇ cm. Not only those particles coated with a metal oxide or metal hydroxide having high whiteness but also metallic powders (e.g., silver, nickel, copper, iron, alloys thereof, etc.) and metallic compounds such as copper sulphide, copper iodide, zinc sulphide, cadmium sulphide and the like, can be employed.
- metallic powders e.g., silver, nickel, copper, iron, alloys thereof, etc.
- metallic compounds such as copper sulphide, copper iodide, zinc sulphide, cadmium sulphide and the like.
- metal oxide particles mention may be made of particles of tin oxide, zinc oxide, copper oxide, cuprous oxide, indium oxide, zirconium oxide, tungsten oxide, etc. Most metal oxides are insulators or semi-conductors and do not show enough conductivity to satisfy the object of the present invention. However, the conductivity is increased, for example, by adding a small amount (not more than 50%, particularly not more than 25%) of a proper secondary component (impurity) to the metal oxide, whereby conductive metal oxide powders having sufficient conductivity to satisfy the object of the present invention can be obtained.
- a secondary component i.e., a conductivity modifier
- antimony oxide can be used for tin oxide, and also oxides of aluminum, gallium, indium, germanium, tin and the like for zinc oxide.
- particles wherein a conductive film of the above-described metal oxides or other metallic compounds is formed on surfaces of non-conductive inorganic particles such as titanium oxide, zinc oxide, magnesium oxide, tin oxide, iron oxide, silicon oxide, aluminum oxide and the like, also can be used.
- non-conductive inorganic particles such as titanium oxide, zinc oxide, magnesium oxide, tin oxide, iron oxide, silicon oxide, aluminum oxide and the like.
- conductive particles which is obtained by mixing tin-oxide-coated titanium oxide particles with antimony oxide and firing the resulting mixture.
- the conductivity of the conductive metal oxide particles is preferred to be not more than about 104 ⁇ cm, particularly not more than about 102 ⁇ cm, most preferably not more than about 101 ⁇ cm in specific resistance in the powdery state.
- the particles having about 102 ⁇ cm ⁇ 10 ⁇ 2 ⁇ cm are obtained and can be suitably applied to the object of the present invention.
- the particles more excellent in conductivity are more preferable.
- the specific resistance (volume resistivity) is measured by charging 5 g of a sample into an insulative cylinder having a diameter of 1 cm and applying a pressure of 200 kg to the cylinder from the top by means of a piston and applying a direct current voltage (for example, 0.001-1,000 V, current of 1 mA or less).
- the conductive particles are preferred to be sufficiently small in the grain size.
- Particles having an average grain size of 1-2 ⁇ m can be used but, in general, those having an average grain size of not more than 1 ⁇ m, particularly not more than 0.5 ⁇ m, most preferably not more than 0.3 ⁇ m, are suitably used.
- grain size used herein means the weight average diameter of single particles. A sample is observed by an electron microscope and is separated into single particles. Diameters (mean values of the long diameter and the short diameter) of about 1,000 particles are measured and classified by a unit of 0.01 ⁇ m to determine the grain size distribution and then the weight average grain size is determined from the following formulae (I) and (II). wherein
- the mixed ratio of the conductive particles in the conductive component depends upon the kind, conductivity, grain size, chain forming ability of particles, and the property, crystallinity, etc. of the polymer binder the particles are mixed with. However, it is generally within a range of about 10-85%, preferably about 20-80%, by weight.
- the mixed ratio of titanium oxide particles coated with a conductive film is generally in the range of about 40-85%, more preferably 50-80%, most preferably 60-80%, by weight.
- thermoplastic polymer to be mixed with the inorganic conductive particles, which forms the conductive component is not particularly limited and can be selected arbitrarily from a host of thermoplastic polymers such as polyamides, polyesters, polyolefins, polyvinyls, polyethers and the like. These polymers are preferred to have fiber-formability from the standpoint of spinning operation. However, even though those polymers deficient in fiber-formability are used, composite filaments can be provided with sufficiently good spinnability by using a fiber-forming thermoplastic polymer as the non-conductive component to be conjugated therewith.
- thermoplastic polymers used for the conductive component particularly preferred are those having a crystallinity of at least 60%, which are poor in compatibility with the non-conductive fiber-forming thermoplastic polymers.
- Such polymers include polyethylene, polypropylene, polyoxymethylene, polyethylene oxide and its derivatives (for example, ethylene oxide/ethylene terephthalate block copolymers), polyvinyl alcohol, polypivalolactone, polycaprolactone, etc.
- polyethylene, polypropylene polyoxymethylene, and copolymers thereof are particularly suitable.
- the conductive component is preferred to have a specific resistance (volume resistivity) of less than 107 ⁇ cm, more preferably not more than 104 ⁇ cm, and not more than 102 ⁇ cm is particularly preferred.
- dispersants for example, waxes, polyalkylene oxides, various surfactants, organic electrolytes, etc.
- coloring agents for example, waxes, polyalkylene oxides, various surfactants, organic electrolytes, etc.
- coloring agents for example, pigments, stabilizers (antioxidants, ultraviolet ray absorbents, etc.) flow improvers and other additives.
- any spinnable polymers can be used.
- spinnable polymers polyamides such as nylon-6, nylon-66, nylon-12, nylon-610 and the like, polyesters such as polyethylene terephthalate, polyethylene oxybenzoate, polybutylene terephthalate and the like, polyacrylonitrile and copolymers and modified polymers thereof, are particularly suitable.
- additives such as delustrants, pigments, coloring agents, stabilizers, antistatic agents (such as polyalkylene oxides, various surfactants or the like).
- the non conductive component composed of a fiber-forming thermoplastic polymer as described above is preferred to have a specific resistance of at least 107 ⁇ cm.
- the conductive core and conductive path usually have substantially the same composition.
- the thermoplastic polymer composition in the conductive path consists of a mixture of the polymer for the non-conductive sheath component with the polymer composition for the conductive core component.
- the mixing ratio of the both components is not specifically limited. However, a mixing ratio such as to bring the content in the mixture of the conductive inorganic particles into the range of 3-50%, particularly 5-40%, by weight, is preferred. If the content is too large, the composite filaments too much increase in metal abrasive property, while, if too small, the antistatic property becomes insufficient.
- the mixture is preferred to occupy at least the exposed portion on filament surfaces of the conductive path.
- the above-described polymer mixture can be produced according to any known processes.
- a process for mixing by means of a static mixer composed of relatively a few, preferably 1-3 mixing elements which is provided in a polymer flow path inside a spinneret assembly (FIG. 12), a mechanical mixer such as an impeller or rotor (FIG. 13), a hydrodynamic mixing utilizing collision of fluids caused by high pressure injection or a breaker such as glass beads or a filter layer provided in the flow path (FIG. 14), etc., and combinations thereof.
- a static mixer composed of relatively a few, preferably 1-3 mixing elements which is provided in a polymer flow path inside a spinneret assembly (FIG. 12), a mechanical mixer such as an impeller or rotor (FIG. 13), a hydrodynamic mixing utilizing collision of fluids caused by high pressure injection or a breaker such as glass beads or a filter layer provided in the flow path (FIG. 14), etc., and combinations thereof.
- the numeral 101 denotes an entrance for a fiber-forming thermoplastic polymer; 102, an entrance for a conductive component polymer composition; 103, a static mixer; 104, a kneader; 105, a mixing zone; 106-108, meeting points; 109, a constriction device, and 110, a spinneret.
- the fiber-forming thermoplastic polymer and conductive component polymer composition to be mixed with each other are preferred to be mutually incompatible. Such a combination provides a mixture in a mutually phase-separated state.
- an unevenly mixed state for example, a fine archipelagic or multi-layeredly dispersed state is preferred from the viewpoint of corona discharging.
- the thick conductive core having a thickness of not less than 5 ⁇ m and a specific resistance of, for example, not more than about 107 ⁇ cm, extending continuously along the entire length of the filament, is considered to make movements in the longitudinal direction of the electric charge easy.
- This function since the conductive core has a thickness larger than a certain degree, will not be deteriorated in processes such as drawing, false-twisting, rewinding, knitting, weaving and the like.
- the conductive path conjoined with the thick conductive core reaches its tip up to or close to the surface of the filament and is exposed lengthwise intermittently, when the filaments are electrified, destaticization by corona discharge is considered to occur at a low potential.
- composite filaments of the present invention in a very small amount, fibrous articles provided with an excellent antistatic property can be produced without impairing aesthetic appearance, such as apparels, lingerie, foundations, hosiery, particularly working clothes for clean rooms, sheetings, carpets, upholsteries, interior cloths, or the like.
- the composite filaments of the invention may be mixed with other natural fibers or artificial fibers and used as continuous filament yarns, staple fibers, in a non-crimped, crimped, undrawn or drawn form.
- the antistatic property was evaluated according to the following method.
- An ordinary nylon-6 drawn yarn (210 deniers/54 filaments) was knit on a circular knitting machine, incorporating a conductive composite filament yarn in every eleventh course, to prepare a tubular knitted fabric mixed with 0.85% based on the weight of the fabric of the conductive composite filaments.
- the resulting fabric in which oils were removed by scouring was thoroughly washed with water, then dried at 80°C for 3 hours and further conditioned at 25°C in an atmosphere of 30% R.H. for 6 hours. Thereafter, the fabric was rubbed 15 times with a cotton cloth at the same temperature and humidity as the above, and the electrified charge after 10 seconds was measured.
- the metal abrasive property was measured by the time required for breaking a stainless steel wire having a diameter of 35 ⁇ m, when the filament yarn traveled on the stainless steel wire at a speed of 100 m/min. (The yarn tension before contacting was 4-5 g and the contact angle was 45°).
- the electric resistance was measured of a yarn consisting of 5 single filaments having a length of 10 cm. Both ends of the yarn were bonded to metal terminals with a conductive adhesive (Dodite D-550, manufactured by Fujikura Kasei K.K.), 10 V of direct current was applied between both the terminals, and the electric resistance was determined. The specific resistance of the conductive component was calculated from the above obtained value of the filament yarn.
- a conductive adhesive Dodite D-550, manufactured by Fujikura Kasei K.K.
- Conductive particles having an average grain size of 0.25 ⁇ m and a specific resistance of 6.3 ⁇ cm were obtained by firing a mixture of titanium oxide particles coated with a tin oxide film and 0.75% by weight of said particles of antimony oxide. Seventy-five parts by weight of the above obtained particles and 25 parts by weight of polyethylene having a molecular weight of 80,000 were kneaded together to prepare a conductive polymer composition A1. This conductive polymer composition A1 and nylon-6 having a relative viscosity in 95% conc.
- H2SO4 of 2.3 were simultaneously spun from orifices having a diameter of 0.25 mm at a spinning temperature of 280°C into composite filament yarns having cross-sectional figures as shown in Table 1, with a conjugated ratio of 1/9 (areal ratio in cross section).
- the as-spun yarns were taken up on a bobbin at a rate of 800 m/min., while cooling and oiling. Then the taken-up filament yarns were drawn at a draw ratio of 2.6 times on a hot roll at 80°C, further contacting with a plate heater at 170°C, to produce drawn yarns Y1 ⁇ Y5 of 20 deniers/3 filaments which were wound up on a pirn.
- any of the yarns Y1 ⁇ Y5 had a specific resistance of not more than the order of 103 ⁇ cm and exhibited good conductivity.
- the yarns Y1 ⁇ Y3 and Y5 had good antistatic properties but the yarn Y4 that had not exposed the conductive polymer component on the filament surface was poor in antistatic property.
- the yarns Y1 ⁇ Y4 had a little metal abrasive property but the yarn Y5 exposing the conductive component largely in width on the surface of the filament had an extremely increased metal abrasive property.
- the yarn Y5 could not be stably manufactured due to increased abrasion of thread guides.
- the yarns Y1 ⁇ Y4 were respectively plied with a nylon-6 filament yarn of 2,600 deniers/140 filaments and the plied yarns were crimped by texturizing.
- a tufted carpet (looped, the mixed ratio of the conductive filaments: 0.17%) was produced.
- a charged voltage of a human body generated when a man putting on leather shoes walked on the resulting carpet in a room at 25°C with 20% R.H. was measured.
- the charged voltages of the carpets incorporated with the yarns Y1 ⁇ Y3 of the present invention were -2.0 kV, -2.3 kV and -1.8 kV, respectively.
- a polyethylene terephthalate polymer having a molecular weight of 15,000 blended with 0.65% based on the weight of the polymer of titanium oxide as a delustrant was used as a non-conductive polymer and the conductive polymer composition A1 prepared in EXAMPLE 1 was used as a conductive polymer composition.
- These polymers were conjugated, in a spinneret, in side by side relation having a cross-sectional figure as shown in FIG. 3, and spun from orifices having a diameter of 0.3 mm at a spinning temperature of 285°C. After quenching and oiling, the as-spun filament yarn was wound up on a take-up roll at a rate of 1,000 m/min.
- Titanium oxide particles coated with tin oxide (SnO2) and 1.5% based on the weight of the particles of antimony oxide were mixed together and fired to produce conductive particles having an average grain size of 0.25 ⁇ m, a content of tin oxide of 15% by weight, a specific resistance of 7 ⁇ cm and a whiteness, i.e., light reflection, of 83%.
- Seventy five parts by weight of the produced conductive particles and 25 parts by weight of a low density polyethylene having a molecular weight of about 50,000 and a melting point of 103°C were mixed and kneaded uniformly together with 0.5 parts by weight of magnesium stearate (a flow improver) to prepare a conductive polymer composition that was denoted as A2.
- Nylon-6 having a molecular weight of about 16,000 and a melting point of 215°C admixed with 0.8% based on the weight of the nylon of titanium oxide to prepare a polymer B1.
- the conductive polymer A2 and the polymer B1 were conjugate-spun with a conjugate ratio of 9/1 at a spinning temperature of 280°C from orifices having a diameter of 0.25 mm into composite filaments having cross-sectional figures as shown in Table 3.
- the as-spun filament yarns were wound up on a take-up roll at a rate of 800 m/min., while quenching and oiling. Then the yarns were drawn 2.6 times their original lengths with a hot roll at 80°C, further brought into contact with a plate heater at 170°C, and wound up on a pirn. Thus, drawn yarns Y10 ⁇ Y13 of 18 deniers/1 filament were obtained.
- any of the yarns Y10 ⁇ Y13 had a specific resistance of the order of 103 ⁇ cm and exhibited good conductivity.
- the yarns Y10, Y12 and Y13 had a good antistatic property of not more than 2.0 kV, but the yarn Y11 whose conductive polymer component was not exposed on the surface of the filaments had a poor antistatic property. Further, the yarns Y10 and Y11 had a decreased metal abrasive property, while the yarns Y12 and Y13 showed a considerably increased metal abrasive property.
- the yarns Y12 and Y13 abraded travellers so remarkably during draw-twisting operation that the stable manufacture of the yarns could not be performed.
- the yarn Y10 was the only yarn that had a good antistatic property as well as a decreased metal abrasive property.
- Titanium oxide particles coated with tin oxide and 0.75% based on the weight of the particles of antimony oxide were mixed together and fired to produce conductive particles having an average grain size of 0.25 ⁇ m and a specific resistance of 6.3 ⁇ cm.
- Seventy-five parts by weight of the produced conductive particles and 25 parts by weight of a polyethylene having a molecular weight of 80,000 were mixed and kneaded together to prepare a conductive polymer composition A3.
- a spinning machine provided with a static mixer comprising a couple of mixing elements in a spinneret assembly such as shown in FIG. 12, 10 parts by volume of the above conductive polymer A3 and 90 parts by volume of a nylon-6 (N1) having a relative viscosity in 95% conc. H2SO4 of 2.3 were spun from orifices having a diameter of 0.25 mm at a spinning temperature of 280°C to form filaments with cross-sectional figures and mixing ratios as shown in Table 5.
- the polymers N1 and A3 were introduced from the entrances 101 and 102, respectively, and the constriction devices 109 were adjusted to control the mixing ratio.
- the as-spun filament yarns were wound up on a take-up roll at a rate of 800 m/min., while quenching and oiling. Then the yarns were drawn 2.6 times their original lengths with a hot roll at 80°C, further brought into contact with a plate heated at 170°C, and wound up on a pirn. Thus, drawn yarns Y18 ⁇ Y20 of 20 deniers/3 filaments were obtained.
- any of the yarns Y18 ⁇ Y20 had a specific resistance of the order of 102 ⁇ cm and exhibited good conductivity.
- the yarns Y18 and Y20 had a good antistatic property but the yarn Y19 whose conductive polymer component was not exposed on the surface of the filaments had a poor antistatic property.
- the yarns Y18 and Y19 had a decreased metal abrasive property, while the yarn Y20 showed a considerably increased metal abrasive property and could not be manufactured stably due to abrasion of thread guides.
- the yarns Y18 and Y19 were respectively plied with a nylon-6 yarn of 2,600 deniers/140 filaments and the plied yarns were crimped by texturizing.
- a tufted carpet (looped, the mixed ratio of the conductive filaments: 0.17%) was produced.
- a charged voltage of a human body generated when a man putting on leather shoes walked on resulting carpet in a room at 25°C with 20% R.H. was measured.
- the charged voltage of the carpet incorporated with the yarn Y18 of the present invention was -2.1 kV.
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Claims (12)
- Filament composite conducteur unitaire comprenant :(a) un composant non-conducteur constitué d'un polymère thermoplastique formé en fibres, formant une enveloppe s'étendant sur la longueur entière du filament, et(b) un composant conducteur qui est constitué d'une âme conductrice et d'un trajet conducteur, enroulé dans et se prolongeant dans le sens de la longueur de ladite enveloppe, l'âme conductrice étant constituée d'un mélange d'un polymère thermoplastique avec des particules conductrices inorganiques, ledit trajet conducteur ayant une composition qui est la même ou qui est différente de l'âme conductrice, comprenant un polymère thermoplastique et des particules conductrices inorganiques,qui est caractérisé en ce qu'en section transversale, ledit composant conducteur présente une forme du type têtard qui est constituée de la tête de l'âme conductrice ayant une épaisseur qui n'est pas inférieure à 5 µm et de la queue du trajet conducteur s'étendant latéralement à partir d'une partie de la périphérie de la tête de l'âme conductrice, transversalement à l'enveloppe, jusqu'à ou à proximité de la circonférence extérieure de l'enveloppe et en ce que le trajet conducteur est exposé par intermittence suivant l'axe longitudinal du filament et n'a pas une largeur supérieure à 1,5 µm sur la surface de la périphérie extérieure de l'enveloppe.
- Filament selon la revendication 1, dans lequel la tête occupe au moins 60 % de la surface du composant conducteur.
- Filament selon la revendication 1, dans lequel le trajet conducteur est exposé sur une largeur non supérieure à 1 µm et sur une longueur non supérieure à 50 % de la longueur totale du filament.
- Filament selon la revendication 1, dans lequel en section transversale ledit composant conducteur occupe de 3 à 40 % de la surface du filament.
- Filament selon la revendication 1, dans lequel ledit trajet conducteur a la même composition que l'âme conductrice.
- Filament selon la revendication 1, dans lequel ledit trajet conducteur comprend un mélange de polymère thermoplastique formé en fibres constituant le composant non-conducteur avec le mélange constituant l'âme conductrice.
- Filament selon la revendication 1, dans lequel ledit composant conducteur présente une résistance spécifique non supérieure à 10⁴ Ω.cm.
- Filament selon la revendication 7, dans lequel la résistance spécifique n'est pas supérieure à 10² Ω.cm.
- Filament selon la revendication 1, dans lequel le polymère thermoplastique formé en fibres est un polymère linéaire synthétique organique choisi dans le groupe constitué du nylon-6, nylon-66, nylon-12, nylon-610, polyéthylène téréphtalate, polyéthylène oxybenzoate, polybutylène téréphtalate et copolymères et polymères modifiés de ceux-ci.
- Filament selon la revendication 1, dans lequel les polymères thermoplastiques contenus dans le composant conducteur sont des polymères linéaires synthétiques organiques choisis dans le groupe constitué du polyéthylène, polypropylène, polyoxyméthylène, et des copolymères de ceux-ci.
- Article fibreux antistatique qui comporte 0,01 à 5 % en poids d'un filament selon la revendication 1.
- Article fibreux selon la revendication 11, qui est un tapis.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62020860A JPS63190017A (ja) | 1987-01-30 | 1987-01-30 | 制電性複合繊維 |
JP20860/87 | 1987-01-30 | ||
JP62069454A JPS63235525A (ja) | 1987-03-23 | 1987-03-23 | 導電性複合繊維 |
JP69454/87 | 1987-03-23 | ||
JP306233/87 | 1987-12-02 | ||
JP62306233A JPH01148811A (ja) | 1987-12-02 | 1987-12-02 | 導電性複合繊維の製造方法 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0276756A2 EP0276756A2 (fr) | 1988-08-03 |
EP0276756A3 EP0276756A3 (en) | 1990-02-21 |
EP0276756B1 true EP0276756B1 (fr) | 1994-04-06 |
Family
ID=27283201
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88100844A Expired - Lifetime EP0276756B1 (fr) | 1987-01-30 | 1988-01-21 | Filaments composites conductifs et articles fibreux contenant ces filaments |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0276756B1 (fr) |
KR (1) | KR900008725B1 (fr) |
CA (1) | CA1285358C (fr) |
DE (1) | DE3888856T2 (fr) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0343496B1 (fr) * | 1988-05-27 | 1994-08-31 | Kuraray Co., Ltd. | Filament composé conducteur et procédé pour sa fabrication |
JP2635139B2 (ja) * | 1988-12-28 | 1997-07-30 | 花王株式会社 | 吸収性物品 |
DE4110279A1 (de) * | 1991-03-28 | 1992-10-01 | Alfo Ag | Lichtleiter |
DE9108057U1 (de) * | 1991-07-01 | 1991-08-22 | August Mink KG, 7320 Göppingen | Technische Bürste mit walzen- oder leistenförmigem Bürstenkörper und entsprechend den jeweiligen Einsatzzwecken auch unterschiedlichsten Beborstungsformen |
AU5008896A (en) * | 1995-03-13 | 1996-10-02 | Arjo Wiggins S.A. | Security paper with conductive fibres detectable by microwave radiation and method for making same |
FR2734584B1 (fr) * | 1995-05-24 | 1997-08-14 | Arjo Wiggins Sa | Papier contenant des elements de securite metalliques et non magnetiques |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU503665B1 (en) * | 1977-08-08 | 1979-09-13 | Kanebo Limited | Conductive composite filaments |
CA1158816A (fr) * | 1980-06-06 | 1983-12-20 | Kazuo Okamoto | Filaments conducteurs composites, et methode de production connexe |
-
1988
- 1988-01-14 CA CA000556540A patent/CA1285358C/fr not_active Expired - Lifetime
- 1988-01-21 DE DE3888856T patent/DE3888856T2/de not_active Expired - Lifetime
- 1988-01-21 EP EP88100844A patent/EP0276756B1/fr not_active Expired - Lifetime
- 1988-01-30 KR KR1019880000844A patent/KR900008725B1/ko active Pre-grant Review Request
Also Published As
Publication number | Publication date |
---|---|
DE3888856T2 (de) | 1994-08-18 |
EP0276756A2 (fr) | 1988-08-03 |
KR880009536A (ko) | 1988-09-15 |
EP0276756A3 (en) | 1990-02-21 |
KR900008725B1 (ko) | 1990-11-27 |
CA1285358C (fr) | 1991-07-02 |
DE3888856D1 (de) | 1994-05-11 |
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